ES2273103T3 - USE OF TRANSITION METAL COMPLEXES AS WHITENING CATALYSTS. - Google Patents

Abstract

Use of certain transition metal complexes with nitrogenous ligands as a catalyst for peroxygenated compounds, characterized in that the transition metal complexes have the formula (1) M (L) nXm (1) meaning M an atom of a metal taken between the set formed by Mn, Fe, Co, Ni, Mo, W, L a ligand taken from the group consisting of pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine or lutidine, which are unsubstituted or may be substituted with one or two C1-C4 alkyl groups. X chloride, bromide, nitrate, perchlorate, sulfate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of an organic acid with 1 to 22 carbon atoms, n means a number from 2 to 4 and m means a number from 0 to 4.

Description

Use of metal complexes of transition as bleaching catalysts.

The present invention relates to the use of certain complex transition metal compounds for the strengthening of the bleaching effect of peroxygenated compounds by bleach color spots on both textile materials and also on hard surfaces, as well as washing agents and cleaning, which contain such complex compounds.

Certain inorganic peroxygenated compounds, in particular hydrogen peroxide and peroxygenated compounds solids, which dissolve in water mediating peroxide release from hydrogen, such as sodium perborate and sodium carbonate perhydrate, have long been used as agents of oxidation for disinfection and bleaching purposes. The effect of Oxidation of these substances depends, in dilute solutions, on great way of temperature; thus, for example with H 2 O 2 or a perborate, is obtained in alkaline baths of treatment of bleaching, only at temperatures above approximately 80 ° C, a sufficiently rapid bleaching of dirty textile materials.

At lower temperatures, the effect of oxidation of inorganic peroxygenated compounds can be improve by adding the so-called agents bleach activators. For this, in the past they set out numerous compounds, especially from the classes of substances of the N- or O-acyl compounds, by example alkylene diamines acylated multiple times, in particular tetraacetyl glycoluryl, hydantoins N-acylated, hydrazides, triazoles, hydrotriazines, urazoles, diketo-piperazines, sulfuryl amides and cyanurates, in addition to carboxylic acid anhydrides, in particular phthalic acid anhydride and substituted anhydrides of maleic acid, esters of carboxylic acids, in particular nonanoyloxy benzene sulphonate sodium (NOBS), isononanoyloxybenzene sulphonate sodium (ISONOBS) and acylated derivatives of sugars, such as pentaacetyl glucose. By adding these substances, the bleaching effect of solutions can be increased aqueous peroxides, to such an extent that at temperatures located around 60 ° C, they are essentially the same effects than with the peroxide solution alone at 95 ° C.

In the effort to obtain washing procedures and bleaching that are energy saving, in recent years they have importance of operating temperatures located manifestly below 60 ° C, in particular below 45 ° C until you reach the cold water temperature.

In the case of these low temperatures, the effect of the activating compounds known so far generally decreases in a recognizable manner. Therefore, there has been no lack of efforts to develop more effective activators for this temperature range, without success being reported to date.
convincing.

A starting point for this is established through the use of transition metal salts and their complex compounds, such as those described, for example, in European patent documents EP 0.392.592, EP 0.443.651, EP-1,001,009, in the international patent application document WO 2004/0399932, in the US patent document US 6,139,769, and in documents EP 0.458.397, EP 0.544.490 or EP 0.549 .271. EP 0.272.030 describes cobalt (II) complexes with ammonia ligands, which may also have other arbitrary mono-, bi-, tri- or tetra-dentate ligands, as activators for H2O. 2}, for use in washing or bleaching agents of textile materials. WO 96/23859, WO 96/23860 and WO 96/23861 describe the use of corresponding Co (III) complexes in automatic dishwashing agents. From EP 0.630.964 certain manganese complexes are known, which certainly have no pronounced effect in terms of a reinforcement of the bleaching of peroxygenated compounds and which do not discolor dyed textile fibers, but which in turn can produce the bleaching of dirt or dye, which has detached from the fibers and is found in washing liquors. From German patent document DE 44.16.438, manganese, copper and cobalt complexes are known, which can carry selected ligands from a large number of sets of substances, and which should be used as bleaching and oxidation catalysts. WO 97/07191 proposes manganese, iron, cobalt, ruthenium and molybdenum complexes with Salen-type ligands, as activators for peroxygenated compounds in hard surface cleaning solutions. EP 1,225,215 describes the use of transition metal complexes, which contain oxime ligands, as a catalyst for compounds.
peroxygenated

The present invention aims at improvement of the effect of oxidation and bleaching of compounds peroxygenates, in particular peroxygenated compounds inorganic, at low temperatures below 80ºC, particularly in the temperature range of about 10 ° C to 45 ° C. The metal complexes required for this should Be easily accessible and simple to prepare.

Surprisingly, he finally found that certain transition metal complexes, consisting of in a simple way, with nitrogen ligands, they contribute manifestly to the cleaning performance against stains in color, found in textile materials or on surfaces hard.

       \ newpage
    

The use of transition metal complexes with nitrogen ligands such as bleaching catalysts for peroxygenated compounds, characterized in that transition metal complexes have the formula (1)

(1) M (L) n X_m

meaning

M

an atom of a metal taken between the set formed by Mn, Fe, Co, Ni, Mo, W,

L

a ligand taken between the set formed by the nitrogen heterocycles

X

chloride, bromide, nitrate, perchlorate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of an acid organic with 1 to 22 carbon atoms, n means a number from 2 to 4 and m means a number from 0 to 4.

These transition metal complexes are used in washing, bleaching and cleaning agents, which contain peroxygenated compounds, in particular in the washing of materials textiles and cleaning agents for hard surfaces, in particularly for crockery, and in solutions for bleaching color spots.

Preferably complexes of the formula (1) with transition metal central atoms in the oxidation stages +2, +3 or +4, as well as complexes with manganese or iron as central atoms.

Examples of ligand L are pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine, lutidine or similar nitrogen heterocycles, which they are unsubstituted, or they can be substituted with one or two groups C 1 -C 4 alkyl.

For X ligands they are used in particularly halides such as chloride, bromide and iodide, next to these however also nitrate, sulfate, perchlorate, ammonia, as well as complex anions, such as tetrafluoroborate and hexafluorophosphate or carboxylic acid anions C 1 -C 22 organic, such as citrates, acetates, propionates, butyrates, hexanoates, octanoates, a nonanoate and a laurate. Anionic ligands procure the compensation of electrical charges between the central atom of a metal Transition and ligand system.

Especially preferred complexes are compounds of the structure Fe (L) 2 X 2 or Mn (L) 2 X 2 such as bis (pyridine) dichloro-iron (II), bis (pyridine) dichloro-manganese (II), such as bis (morpholine) dichloro-iron (II), bis (morpholine) dichloro-manganese (II), bis (methyl imidazole) dichloro-iron (II), bis (methyl imidazole) dichloro manganese (II), bis (ethyl-imidazole) -dichloro-iron (II), bis (ethyl-imidazole) dichloro-manganese (II), bis (pyrazole) dichloro-manganese (II), bis (pyrazole) dichloro-iron (II), bis (pyridine) dibromo-iron (II), bis (pyridine) dibromo-manganese (II), such as bis (pyridine) diacetate-iron (II), bis (pyridine) diacetate manganese (II), as well as Fe (L) 4 X 2 type complexes, Mn (L) 4 X 2.

Corresponding complexes have been described. in the bibliography, for example in the quotes of G. J. Long, D. L. Whitney, and J. E. Kennedy, Inorg. Chemistry, 1971, 10 (7), 1,406-1,410, of H.T. Witteveen, B. Nieuwenhuijse, and J. Reedijk, J. Inorg. Nucl. Chem., 1974, 36, 1535-1.541, and by H. T. Witteveen and J. Reedijk, Solid State Commun., 1973, 12, 557. However, its activity as bleaching catalysts had not been described so far.

As peroxygenated compound they enter consideration, first of all, alkali metal perborates mono- and respectively tetrahydrates and / or alkali metal percarbonates, the alkali metal being sodium favorite. Together with these, they can be used, however, also alkali metal or ammonium peroxosulfates, such as e.g. potassium peroxomonosulfate (technically: Caroat® or Oxone®). The concentration of these peroxygenated compounds in the formulation Overall washing, bleaching and cleaning agent is 5 - 90%, preferably from 10-70%.

The amounts of compounds used peroxygenates are usually chosen in such a way that in the solutions of washing and cleaning agents are present between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm of active oxygen. Also the amount used of a compound bleaching booster complex depends on the purpose of utilization. Depending on the desired degree of activation, it is used in amounts such that 0.01 mmol to 25 are used mmol, preferably 0.1 mmol to 2 mmol of the complex per mole of peroxygenated compound, but in special cases you can also stay above or below these limits. In agents of washing, bleaching and cleaning is preferably contained in 0.0025  at 0.25% by weight, in particular from 0.01 to 0.5% by weight, of complex bleaching booster compound, defined above.

Additionally or alternatively, the agents of washing, bleaching and cleaning may also contain peroxide of hydrogen or oxidizing agents on an organic basis in the concentration range of 1-20%. They all belong known peroxycarboxylic acids, eg acid monoperoxy-phthalic acid dodecane diperoxycarboxylic acid phthalimido-peroxycarboxylic acids, such as PAP and related systems, or the amido-peracids cited in the European patent application document EP-A-170,386.

       \ newpage
    

The concept of money laundering here encompasses both the bleaching of a stain that is on the surface of a textile material as well as the bleaching of a stain that has been detached from the surface of a textile material and it found in the wash treatment bath. For the bleaching of stains on hard surfaces the same is valid in due course. Other potential uses are in the sector of personal care (in English, personal care) eg in the case of hair bleaching and for improving the effectiveness of denture cleaning agents. For the rest, the complexes Metals described are used in industrial laundries, in the wood and paper bleaching, in cotton bleaching and agents disinfectants

In addition, the invention relates to a process for cleaning textile materials as well as hard surfaces, particularly tableware, mediating the use of cited complex compounds in common with peroxygenated compounds in an aqueous solution, which eventually contains other components of washing agents or cleaning agents, as well as agents of washing and cleaning agents for hard surfaces, in particular cleaning agents for dishes, those intended for use being preferred to its use in mechanical procedures, which contain such complex compounds

The use according to the invention consists essentially, in the case of hard surfaces soiled with color spots or in the case of soiled textile materials, in providing conditions, in which a peroxidic oxidation agent and the complex compound can react with each other. of the formula (1), with the aim of obtaining transformation products that act by oxidizing more strongly. Such conditions arise in particular when the participants in the reaction meet each other in an aqueous solution. This can happen by adding separately the peroxygenated compound and the complex of the formula (1) to the aqueous solution of the washing and cleaning agent. However, the process according to the invention is carried out in a particularly advantageous manner by using a washing agent or a hard surface cleaning agent, which contains the complex compound of the formula (1) and possibly an agent of peroxygenated oxidation. The peroxygenated compound can also be added to the solution separately in substance or as a preferably aqueous solution or suspension, when a washing or cleaning agent free of
peroxygen

Washing and cleaning agents, which can be present as granules, solid materials in the form of powders or of tablets, as molded bodies of other types, or as homogeneous solutions or suspensions, may contain, apart from cited bleaching booster metal complex, in principle all known and usual constituent substances in such agents. The agents may contain in particular substances that improve detergency (known as builder), surfactants with surface activity, peroxygenated compounds, activators additional peroxygenates or organic peracids, solvents water-miscible organic, sequestering agents, enzymes as well as special additives with a protective effect of color and fibers Other auxiliary substances are possible, such as electrolytes, pH regulating agents, inhibitors of silver corrosion, foam regulating agents, as well as coloring and perfuming substances.

A cleaning agent for hard surfaces, according to the invention, it may contain, in addition to this, components that they act abrasively, in particular fine quartz powders, wood sawdust, fine powders of synthetic materials, grease and glass microspheres, as well as mixtures of these. The substances abrasives are contained in cleaning agents preferably in a proportion not exceeding 20% by weight, in particular 5 to 15% by weight.

The washing, bleaching and cleaning agents may contain one or more surfactants, in particular anionic surfactants, non-ionic surfactants and mixtures thereof, but also cationic, ionic and amphoteric cationic surfactants. Such surfactants are contained in washing agents according to the invention in quantitative proportions of preferably 1 to 50% by weight, in particular 3 to 30% by weight, contrary to which in hard surface cleaning agents are contained Normally smaller proportions, ie proportions of up to 20% by weight, in particular up to 10% by weight and preferably in the range of 0.5 to 5% by weight. In cleaning agents for use in mechanical dishwashing procedures, poor compounds are normally employed in
foam.

Suitable anionic surfactants are in particular soaps and those containing sulfate or sulphonate groups. Suitable surfactants of the sulphonate type are preferably (C 9 -C 13 alkyl) benzene sulphonates, olefin sulphonates, that is mixtures of alkene and hydroxyalkane sulphonates, as well as disulfonates, such as which are obtained, for example, from monoolefins with a double bond located at one end or inside, by sulfonation with gaseous sulfur trioxide and subsequent hydrolysis under alkaline or acidic conditions of the sulfonation products. Alkane sulphonates are also suitable, which are obtained from C 12 -C 18 alkanes, for example by sulfocloration or sulfooxidation with subsequent hydrolysis or neutralization. Also suitable are esters of alpha-sulfo-fatty acids (ester sulphonates), for example the alpha-sulphonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are prepared by sulfonation of fatty acid methyl esters of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule, and by a subsequent neutralization to give soluble mono-salts in
Water.

       \ newpage
    

Other appropriate anionic surfactants they are esters of glycerol with sulfated fatty acids, which they constitute mono-, di- and tri-esters, as well as mixtures thereof. How alkylsulfates are preferred alkali metal salts, and in particular sodium salts, of Sulfuric acid half esters of fatty alcohols C 12 -C 18, for example alcohol-based coconut fat, tallow fatty alcohol, lauryl alcohol, myristyl, cetyl or stearyl or of the C 8 -C 20 oxo-alcohols, and semi-esters of secondary alcohols with this length of chains. In addition, alkylsulfates of the said chain length, containing a linear alkyl radical synthetic, prepared on the basis of petrochemical products. Appropriate anionic surfactants are also 2,3-alkyl sulfates, which are prepared for example in accordance with US patent documents. US 3,234,158 and US 5,075,041. Monoesters are also appropriate with sulfuric acid from linear or branched alcohols, ethoxylated with 1 to 6 moles of ethylene oxide, such as C 9 -C 11 alcohols branched with methyl in position 2, which have an average of 3.5 moles of ethylene oxide (OE), or C 12 -C 18 fatty alcohols with 1 to 4 OE

Preferred anionic surfactants also include salts of alkyl sulfosuccinic acids, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and which constitute monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain radicals of C 8 -C 18 fatty alcohols or mixtures thereof. As other anionic surfactants, derivatives with fatty acids of amino acids, for example, N-methyl-taurine (taurides) and / or N-methyl-glycine (sarcosinates) come into consideration. As other anionic surfactants, soaps are particularly considered, for example in proportions of 0.2 to 5% by weight. In particular, soaps of saturated fatty acids are suitable, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, as well as in particular from natural fatty acids, for example soaps mixtures that are derived from coconut, palm kernel or fatty acids
tallow.

Anionic surfactants, including Soaps can be presented in the form of their sodium salts, potassium or ammonium, as well as in the form of soluble base salts organic, such as mono-, di- or tri-ethanolamine. Preferably, the anionic surfactants are presented in form of its sodium or potassium salts, in particular in the form of sodium salts The anionic surfactants are contained in washing agents according to the invention preferably in proportions of 0.5 to 10% by weight, and in particularly in proportions of 5 to 25% by weight.

Non-ionic surfactants are used preferably alkoxylated alcohols, advantageously ethoxylated, in particular primaries, which preferably have 8 to 18 atoms of C, and on average 1 to 12 moles of ethylene oxide (OE) per mole of alcohol, in which the alcohol radical can be linear or preferably be branched with methyl in position 2, or may contain linear and branched methyl radicals in a mixture, such as those usually presented in radicals of oxo-alcohols. In particular, they are preferred, not However, ethoxylated compounds of alcohols with linear radicals from naturally occurring alcohols with 12 to 18 C atoms, eg of a coconut, palm kernel, tallow or alcohol fatty alcohol oleyl, and on average with 2 to 8 OE per mole of alcohol. To the preferred ethoxylated alcohols belong, for example, alcohols C 12 -C 14 with 3 OE or 4 OE, alcohols C 9 -C 11 with 7 OE, alcohols C_ {13} -C_ {15} with 3 OE, 5 OE, 7 OE or 8 OE, C 12 -C 18 alcohols with 3 OE, 5 OE or 7 OE, and mixtures of these, such as mixtures of an alcohol C_ {12} -C_ {14} with 3 OE and an alcohol C_ {12} -C_ {18} with 7 OE. The degrees of Ethoxylation indicated represent statistical mean values, which they can be an integer or a fractional number for a special product Preferred alcohol ethoxylated compounds have a narrow distribution of counterparts range ethoxylates, NRE). Additionally to these agents nonionic surfactants, alcohols can also be used fatty with more than 12 OE. Examples of them are fatty alcohols (of tallow) with 14 OE, 16 OE, 20 OE, 25 OE, 30 OE or 40 OE.

Among the nonionic surfactants are they also have alkyl glycosides of the formula general RO (G) x, where R means a radical primary aliphatic, linear or branched with methyl, in particular branched with methyl in position 2, with 8 to 22, preferably 12 to 18 atoms of C, and G represents a unit of glycosa (sugar) with 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as magnitude as must determine analytically, it can also take values fractional - between 1 and 10; preferably, x is between 1.2 and 1.4. Also appropriate are polyhydroxy fatty acid amides of the formula (I),

       \ vskip1.000000 \ baselineskip
    

\uelm{N}{\uelm{\para}{R ^{2} }}

--- Z(I) R1 --- CO ---

 \ uelm {N} {\ uelm {\ para} {R2}} 

--- Z

       \ vskip1.000000 \ baselineskip
    

in which the radical R1 -CO represents an aliphatic acyl radical with 6 to 22 carbon atoms, R2 represents hydrogen, a radical alkyl or hydroxyalkyl with 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxy-alkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Preferably, the polyhydroxy acid amides Fatty are derived from reducing sugars, with 5 or 6 atoms of carbon, in particular of the glucose.

       \ newpage
    

To the set of polyhydroxy fatty acid amides belong also compounds of the formula (II)

one

in which R3 means a alkyl or alkenyl radical, linear or branched, with 7 to 21 atoms carbon, R 4 means a linear alkylene radical, branched or cyclic, or an arylene radical with 6 to 8 atoms of carbon and R 5 means a linear, branched alkyl radical or cyclic, or an aryl radical or a radical oxy-alkyl with 1 to 8 carbon atoms, being preferred C 1 -C 4 alkyl radicals or phenyl, and [Z] represents a radical polyhydroxy-linear alkyl, whose alkyl chain is substituted with at least two hydroxyl groups, or derivatives alkoxylated, preferably ethoxylated or propoxylated, of this radical. [Z] is also preferably obtained in this case. by amination under reducing conditions of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy substituted compounds or N-aryloxy can then be transformed, by example according to WO 95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, in the desired polyhydroxy amides of acids fatty

An additional class of surfactants does not ionic, preferably used, which are used either as single non-ionic surfactant or in combination with others nonionic surfactants, in particular in common with alkoxylated fatty alcohols and / or alkyl glycosides, they are alkyl esters of alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

Agents may also be appropriate. nonionic surfactants of the type of amine oxides, by example of an N-alkyl oxide of coco-N, N-dimethyl amine and an N-alkyl oxide of tallow-N, N-dihydroxyethyl amine, and of the fatty acid alkanol amides.

Among the great set of agents cationic surfactants are particularly preferred compounds hydroxyalkyl-quates (quaternaries) of general structures (III) and (IV).

       \ vskip1.000000 \ baselineskip
    

2

       \ vskip1.000000 \ baselineskip
    

with the radicals R 1, R 2, R 3 = C 1 -C 22 alkyl and n = 1 a 5.

How other surfactants enter consideration of the so-called geminal surfactants (Twins). This concept generally means compounds that have two hydrophilic groups per molecule. These groups are separated from each other, as a rule, by a called spacer (in English "spacer"). This spacer It is, as a rule, a carbon chain, which should be what long enough for hydrophilic groups to have a sufficient distance, so that they can act independently of each other. Such surfactants are generally distinguished by a critical micellar concentration unusually small, and for the ability to reduce greatly The surface tension of the water. They can also be used without However, polyhydroxy fatty acid amides geminals or poly (polyhydroxy acid amides) fatty), such as those described in WO documents 95/19953, WO 95/19954 and WO 95/19955. Other types of agents Surfactants may have dendrimer structures.

A washing agent according to the invention contains preferably at least one detergency builder organic and / or inorganic, soluble in water and / or insoluble in water.

As water-soluble inorganic detergency builder materials, in particular alkali metal silicates and alkali metal polymeric phosphates, which may be present in the form of their alkaline, neutral or sodium or potassium acid alkali salts. Examples are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, the so-called sodium hexametaphosphate, as well as the corresponding potassium salts, or mixtures of sodium and potassium salts. As inorganic, water insoluble and water dispersible detergency builder materials, crystalline or amorphous alkali metal alumosilicates are used in particular, in proportions of up to 50% by weight. Among these, crystalline sodium alumosilicates are preferred in a quality for washing agents, in particular zeolites A, P and possibly X, alone or in mixtures, for example in the form of a concomitantly crystallized material based on zeolites A and X. Its calcium binding capacity is, as a rule, in the range of 100 to 200 mg of CaO per gram. Appropriate detergency enhancing substances are also crystalline alkali metal silicates, which can be presented alone or in admixture with amorphous silicates. The alkali metal silicates, useful as detergency enhancing substances, preferably have a molar ratio of an alkali metal oxide to SiO2 below 0.95, in particular from 1: 1.1 to 1: 12, and can be presented in an amorphous or crystalline form. Preferred alkali metal silicates are sodium silicates, in particular amorphous sodium silicates with a molar ratio of Na 2 O to SiO 2 of 1: 2 to 1: 2.8. As crystalline silicates, which can be presented alone or in admixture with amorphous silicates, crystalline layered silicates of the general formula Na 2 Si x O 2 x + 1 x Y 2 O are preferably used , wherein x, the so-called module, is a number from 1.9 to 4, and y is a number from 0 to 20, and the preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those, in those that x adopts in the aforementioned general formula the values 2 or 3. In particular, both δ- and sodium β-disilicates are preferred (Na2Si2O_ {5} \ cdotY H_ { 2} O). Sodium β-silicates with a module between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04 / 238,809 or JP 04 / 260,610. Almost anhydrous crystalline alkali metal silicates, prepared from amorphous silicates, of the aforementioned general formula, in which x means a number from 1.9 to 2.1, can also be used. In another preferred embodiment of such agents, a crystalline layered sodium silicate with a module of 2 to 3 is used. Crystalline sodium silicates, with a module in the range of 1.9 to 3.5, are used in a further preferred embodiment of agents according to the invention. In a preferred embodiment of the agents according to the invention, a granular composition based on an alkali metal silicate and an alkali metal carbonate is used, as commercially available, for example, under the name Nabion® . In the case where an alkali metal alumosilicate, in particular a zeolite, is also present as an additional detergency enhancing substance, the weight ratio of the alumosilicate to the silicate, in each case referred to the anhydrous active substances, is preferably 1: 10 to 10: 1. In agents, which contain both amorphous and crystalline alkali metal silicates, the weight ratio of the amorphous alkali metal silicate to the crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and in particular of 1: 1 a
twenty-one.

Such detergency builder substances they are contained in agents according to the invention, preferably, in proportions of up to 60% by weight, in particular 5 to 40% in weigh.

To organic substances improving water-soluble detergency belong polycarboxylic acids, in particular citric acid and saccharic acids, acids amino-polycarboxylic acids, in particular acid methyl glycine diacetic acid nitrile-triacetic acid ethylene diamine tetraacetic as well as a poly (aspartic acid).

Acids can also be used polyphosphonics, in particular acid amino-tris (methylene phosphonic), acid ethylenediamine tetrakis (methylene phosphonic) and the acid 1-hydroxyethane-1,1-diphosphonic. Polymeric (poly-) carboxylic acids are also preferred, in particularly polycarboxylates, which are accessible by oxidation of polysaccharides and respectively of dextrins, or acrylic acids, methacrylic acids, polymeric maleic acids and copolymers based on these, which may contain, incorporated in the polymerization, also small proportions of substances polymerizable without any carboxylic acid functionality. The relative molecular mass of carboxylic acid homopolymers unsaturated is usually between 5,000 and 200,000, the of the copolymers is between 2,000 and 200,000, and preferably it is 50,000 to 120,000, in each case referred to acid free. A copolymer of acrylic acid and maleic acid especially preferred has a relative molecular mass of 50,000 to 100,000 They are usual products in commerce, for example, Sokalan® CP 5, CP10 and PA 30 of the BASF entity. Are appropriate also copolymers of acrylic or methacrylic acid with ethers vinyl, such as vinyl methyl ethers, esters vinyl, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. As organic substances water-soluble detergency builders can be used also terpolymers, which contain two acids as monomers unsaturated and / or its salts, as well as, as a third monomer, vinyl alcohol and / or an esterified vinyl alcohol or a hydrate carbon The first acidic monomer, or one of its salts, is derived from a carboxylic acid C 3 -C 8 monoethylenically unsaturated, and preferably of a monocarboxylic acid C 3 -C 4, in particular acid (meth) acrylic.

The second acidic monomer and one of its salts, respectively, may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being especially preferred, and / or a derivative of an allyl sulfonic acid, which it is substituted in position 2 with an alkyl or aryl radical. Such polymers generally have a relative molecular mass between 1,000 and 200,000. Other preferred copolymers are those which preferably have acrolein monomers and a mixture of acrylic acid and salts of acrylic acid and, respectively, acetate
vinyl.

       \ newpage
    

Organic substances improving detergency can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in form of 30 to 50% aqueous solutions. All acids These are used, as a rule, in the form of their salts soluble in water, in particular its metal salts alkaline

Such organic substances improving detergency may be contained, if desired, in some proportions of up to 40% by weight, in particular up to 25% in weight, and preferably 1 to 8% by weight. Some proportions close to said upper limit are preferably used in agents in the form of pastes or liquids, in particular in agents that They contain water.

As detergency builder components, soluble in water, in cleaning agents for hard surfaces, according to the invention, all the principles come into consideration detergency builders that are usually used to the mechanical cleaning of dishes, for example phosphates of alkali metals mentioned above. Your proportions may be located in the range of up to about 60% by weight, in particular of 5 to 20% by weight, referred to the total agent. Others possible water-soluble detergency builder components are, together with polyphosphonates and phosphonate-alkyl carboxylates, by for example, organic polymers of natural or synthetic origin of the type above exposed polycarboxylates, which act as agents concomitant detergency builders in particular in regions with hard water, and hydroxycarboxylic acids that occur in nature, such as for example mono- or acid di-hydroxysuccinic acid alpha-hydroxypropionic and gluconic acid. To the preferred organic components detergency builders the citric acid salts belong, in particular a citrate of sodium. As citrate sodium citrate comes into consideration of anhydrous episode and preferably the episode citrate dihydrate Trisodium citrate dihydrate can be used in form of a fine or coarse crystalline powder. Depending on value of pH, which is adjusted after all in cleaning agents according to the invention, acids can also be presented corresponding to said salts of improving agents of concomitant detergency.

In addition to complex compounds used according to the invention, conventional ones can be used bleaching activating agents, that is compounds that release peroxocarboxylic acids under perhydrolysis conditions. They are appropriate the usual bleaching activating agents, which they contain O- and / or N-acyl groups. They prefer alkylene diamines acylated multiple times, in particular tetraacetyl ethylene diamine (TAED), acylated glycolurils, in particular tetraacetyl glycoluryl (TAGU), acylated derivatives of triazine - in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated phenyl sulphonates, in particular a nonanoil- or isononanoyl-oxy-benzene sulfonate (NOBS or ISONOBS) or its amide derivatives, such as those are described eg in EP 170,386, alcohols acylated plurivalents, in particular triacetin, diacetate of ethylene glycol and 2,5-diacetoxy-2,5-dihydrofuran, as well as acetylated sorbitol and manita, and acylated derivatives of sugars, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl-lactose, as well as a glucamine acetylated, eventually rented in N, and glucono-lactone In addition, they are appropriate for this Purpose of use nitrile-quates compounds (quaternary) open chain or cyclic. Can also be employ combinations of conventional activating agents of the bleaching, which are known from the patent application German DE 44.43.177.

To enzymes eventually contained in the agents according to the invention belong proteases, amylases, pululanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, such amylases such as Termamyl®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or cellulases known from the international patent applications WO 96/34108 and WO 96/34092, and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used may be adsorbed to substances of support and / or embedded in wrapping substances, as described, for example, in patent applications WO 92111347 or WO 94/23005, in order to protect them against premature deactivation. These are contained in washing and cleaning agents according to the invention, preferably in proportions of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes being especially preferred stabilized against oxidation degradation.

\hbox{estar contenida en una proporción de hasta 50% en peso,
preferiblemente de 5 a 40% en peso.}

Preferably, the agents for mechanical dishwashing according to the invention contain the usual alkali metal based supports, such as, for example, alkali metal silicates, alkali metal carbonates and / or alkali metal hydrogen carbonates. Among the alkali metal based supports, usually employed, are carbonates, hydrogen carbonates and alkali metal silicates with a molar ratio of SiO2 / M2O (M = an alkali metal atom) of 1 : 1 to 2.5: 1. Alkali metal silicates may be contained in such cases in proportions of up to 40% by weight, in particular 3 to 30% by weight, based on the total agent. The alkali metal based support system, which is preferably used in the cleaning agents according to the invention, is a mixture of a carbonate and a hydrogen carbonate, preferably sodium carbonate and sodium hydrogen carbonate, which may

 \ hbox {be contained in a proportion of up to 50% by weight,
preferably from 5 to 40% by weight.} 

Another object of the invention is an agent for the mechanical cleaning of dishes, containing 15 to 65% by weight, in particular of 20 to 60% by weight, of components improving water-soluble detergency, 5 to 25% by weight, in particular 8 at 17% by weight, of oxygen-based bleaching agents, in each case referred to the total agent, and from 0.1 to 5% by weight of one or several of the cyclic ketones of sugars defined above. A agent of this type is preferably of low alkalinity, i.e. that its solution in a percentage by weight has a pH value from 8 to 11.5, in particular from 9 to 11.

In an additional embodiment of the agents according to the invention for automatic cleaning of tableware, is contained from 20 to 60% by weight of agents organic, water soluble, detergency builders in particular an alkali metal citrate, from 3 to 20% by weight of a alkali metal carbonate and 3 to 40% by weight of a disilicate of alkali metal

To produce corrosion protection of silver, in the agents for cleaning dishes can be employ agents that inhibit corrosion of silver. Preferred Silver corrosion protection agents are sulfides organic substances such as cystine and cysteine, di- o phenols tri-valent, optionally substituted triazoles with alkyl or aryl such as benzotriazole, isocyanuric acid, salts and / or complexes of titanium, zirconium, hafnium, molybdenum, vanadium or cerium, as well as salts and / or complexes of the metals that are contained in the appropriate complexes according to the invention, with other ligands other than those preset in the formula (I).

If the agents form too much foam in the case of its use, can still be added up to 6% by weight, preferably about 0.5 to 4% in weight, of a foam regulating compound, preferably chosen from the set comprising silicones, paraffins, combinations of paraffins and alcohols, silicic acids hydrophobic, bis (fatty acid amides), as well as their mixtures and other known foam inhibitors, obtainable in commerce. Preferably, the inhibitory agents of the foam, in particular the foam inhibitors that they contain silicones and / or paraffins, they are bound to a substance of granular support, soluble or dispersible in water. Are preferred particularly in this case mixtures of paraffins and a bis-stearyl-ethylene diamide. Other optional constituent substances in agents according to the invention are, for example, perfume oils (essential).

To organic solvents usable in agents according to the invention, in particular when they present in a liquid or pasty form, belong alcohols with 1 at 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and ethers which can be derived from the aforementioned classes of compounds. Such water miscible solvents are present in the agents of cleaning according to the invention preferably in a proportion not greater than 20% by weight, in particular 1 to 15% by weight.

For the adjustment of a desired pH value, which does not establish itself by mixing others components, the agents according to the invention may contain acids compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, acid lactic acid, glycolic acid, succinic acid, glutaric acid and / or acid adipic, but also inorganic acids, in particular acid sulfuric or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulating agents are contained in the agents. according to the invention preferably in a proportion not greater than 10% by weight, in particular 0.5 to 6% by weight.

The agents according to the invention are presented preferably as formulations in the form of powders, granules or in the form of tablets, which can be prepared in a way itself known, for example by mixing, granulation, compaction with rollers and / or by spray drying of the components that can be thermally charged and by adding the more sensitive components, among which are to be counted in particular enzymes, bleaching agents and catalyst Whitening. The agents according to the invention, in the form of solutions aqueous or containing other usual solvents, are prepared from especially advantageous way by a simple mixing of the constituent substances, which can be added in substance or as a solution to an automatic mixer.

For the preparation of particulate agents with a high bulk (bulk) apparent weight, in particular in the range of 650 g / 950 g / l, a process having an extrusion step, known from the document, is preferred European patent EP 0.486.592. An additional preferred preparation, with the aid of a granulation process, is described in European patent document EP 0.642.576. The preparation of agents according to the invention in the form of powders and / or granules, which do not give off dust, stable in storage and capable of slipping, with high apparent densities, located in the range of 800 to 1,000 g / l, can be carried out also by mixing, in a first stage of the process, the detergency builder components with at least a certain proportion of liquid components of the mixture, mediating increase in the apparent density of this pre-mix, and then - if desired after drying intermediate - combining the other components of the agent, including the bleaching catalyst, with the previous mixture obtained from this
way.

For the preparation of agents compliant with invention in the form of tablets, preferably proceeding by mixing with each other all the components in a mixer and compressing the mixture by means of habitual presses to form tablets, by example eccentric presses or rotary presses, with pressures of compression located in the range of 200 · 10 5 Pa a 1,500 · 10 5 Pa. In this way, they are obtained without problems tablets resistant to breakage and that nevertheless dissolve quickly enough in the conditions of use, with some flexural strengths normally located above 150 N. Preferably, a tablet produced in this way has a weight from 1 to 5 g to 40 g, in particular from 20 g to 30 g, with a diameter from 3 to 5 mm up to 40 mm.

Examples Example 1 Synthesis of bis (pyridine) dichloro-manganese (II) Mn (py) 2 Cl 2 (Cat 1)

5.7 g (0.045 mol) of chloride Manganese (II) was dissolved in 400 ml of ethanol and the solution was mixed with 49 g (0.62 mol) of pyridine (pyridine was previously dried over KOH). The reaction mixture was heated to reflux for four hours. The suspension obtained was filtered at 60 ° C and the isolated solid material was washed consecutively with 100 ml of a 10% isopropanolic solution of pyridine, as well as with 100 ml of petroleum benzine (50-70 ° C). After a vacuum drying, 12.5 g of a complex of beige color, which corresponds to a yield of 97.5%.

Analytical Data:

Elementary analysis for C 10 H 10 N 2 Cl 2 Mn (284.86 g / mol);

calculated: C 42.2% H 3.5% N 9.8% Cl 24.9% Mn 19.3% found: C 42.2% H 3.1% N 9.5% Cl 25.0% Mn 19.8%

       \ vskip1.000000 \ baselineskip
    

Example 2

Synthesis of bis (pyridine) dichloro-iron (II) Fe (py) 2 Cl 2 (Cat 2)

6.0 g (0.047 mol) of chloride iron (II) was dissolved in 400 ml of ethanol, then The solution was mixed with 49 g (0.62 mol) of pyridine (pyridine it was previously dried over KOH). The transparent, colored solution Intense yellow, allowed to stand for 12 hours at the temperature ambient, after this the material was filtered off yellow precipitated solid, and washed with 50 ml of benzine of oil (50-70ºC). After a drying in empty, 9.9 g of an orange complex were obtained yellowish, which corresponds to a yield of 73.9%.

Analytical Data:

Elementary analysis for C 10 H 10 N 2 Cl 2 Fe (284.94 g / mol);

calculated: C 42.2% H 3.5% N 9.8% Cl 24.9% Faith 19.3% found: C 42.1% H 3.3% N 9.8% Cl 25.5% Faith 19.6%

       \ vskip1.000000 \ baselineskip
    

Example 3

Synthesis of bis (methyl-imidazole) dichloro-manganese (II) Mn (Melm) 2 Cl 2 (Cat 3)

44 g (0.54 mol) of N-methyl-imidazole dissolved in 400 ml of methanol Then, 33 g (0.26 mol) of manganese chloride (II), which dissolved almost completely. Be subsequently stirred for one hour at room temperature, after this the color precipitate was filtered off of course it had separated, and washed twice in each case with 25 ml of petroleum benzine (30-60 ° C). After a vacuum drying, 18.9 g of the color complex were obtained off-white gray This corresponds to a yield of 25.1%.

Analytical Data:

Elementary analysis for C 8 H 12 N 4 Cl 2 Mn (290.0 g / mol);

calculated: C 33.13% H 4.17% N 19.32% Cl 24.45% Mn 18.93% found: C 33.25% H 4.40% N 19.05% Cl 24.5% Mn 18.7%

       \ vskip1.000000 \ baselineskip
    

Example 4

Synthesis of bis (morpholine) dichloro-manganese (II) Mn (mopln) 2 Cl 2 (Cat 4)

22.7 g (0.32 mol) of morpholine dissolved in 400 ml of methanol. Then, 20.0 g of manganese chloride (II), which dissolved almost completely. Be subsequently stirred for 4 hours at room temperature, after this the precipitated material was filtered off light color, and washed twice in each case with 25 ml of benzine of oil (30-60ºC). After a drying in empty, 17.2 g of the whitish brown complex were obtained. This corresponds to a yield of 36.3%.

Analytical Data:

Elementary analysis for C 8 H 16 N 2 Cl 2 Mn (298.07 g / mol);

calculated: Cl 23.8% found: Cl 23.5%

       \ vskip1.000000 \ baselineskip
    

Example 5

Synthesis of bis (ethyl-imidazole) dichloro-manganese (II) Mn (eimid) 2 Cl 2 (Cat 5)

51.9 g (0.54 mol) of 2-ethyl-imidazole dissolved in 400 ml of methanol Then, 33.0 g of chloride were added of manganese (II), which dissolved almost completely. It stirred subsequently for 4 hours at room temperature, then from this the resulting brown solution was concentrated by means of a rotary evaporator. In this case crystals precipitated fine, these were filtered off and washed twice in each case with 25 ml of propanol. After a vacuum drying, 27.2 g of the whitish brown complex were obtained. This corresponds to a yield of 32.8%.

Analytical data

Chlorine analysis for C 10 H 14 N 4 Cl 2 Mn (316.1 g / mol);

calculated: Cl 22.1% found: Cl 22.7%

       \ vskip1.000000 \ baselineskip
    

Example 6

Bleaching performance

The bleaching performance of Cat compounds 1 to Cat 5 according to the invention was tested in comparison to the TAED bleaching activating agent. For this, 10 were dissolved mg / l of the catalyst in a wash liquor, prepared by 2 g / l solution of an agent-free base washing agent of bleaching (WMP, from WFK, Krefeld, Germany). After having 1 g / l of sodium percarbonate (from Degussa entity) added, carried out the washing tests on a Linitest device (of the Heräus entity) at 20-40ºC. The time period of washing was 30 min., and the water hardness of 18ºdH (dH = hardness German). Tea was used as a bleaching test tissue cotton (BC-1) and curry on cotton (BC-4, both from WFK, Krefeld). As a result of bleaching was evaluated for the difference in remissions, measured with a Elrepho apparatus, after washing, compared to non-tissue washed. As comparison test (V1), instead of the 10 mg / l amount of a catalyst, in each case 250 mg / l of TAED

       \ vskip1.000000 \ baselineskip
    

Compound Remission Difference (ddR %) 20ºC 40 ° C BC-1 BC-4 BC-1 BC-4 Cat one 3.6 1.5 5.7 3.0 Cat 2 3.8 2.9 4,5 3.6 Cat 3 3.8 1.4 8.1 3.9 Cat 4 2.8 1.6 7.0 3.7 TAED (V1) 2.5 1.1 4.0 2.4

       \ vskip1.000000 \ baselineskip
    

It is recognized that, through the compounds according to the invention (Cat 1 to Cat 5), a bleaching effect significantly better than by conventional TAED bleaching activating agent in a essentially higher concentration (V1 = comparative 1). Be they obtained essentially identical results when the Sodium percarbonate was replaced by sodium perborate.

Example 7 PH dependence on bleaching performance

The tests were carried out analogously to Example 6, but with the addition of 0.5 g / l hydrogen peroxide instead of perborate at a constant pH value in the glass of precipitates

Compound Remission Values (ddR %) value of pH 7 8 9 10 eleven 12 Cat one 0.1 1.2 4.8 8.8 9.2 4,5

The results show that the compounds according to the invention have an optimum bleaching located in the pH range from 9 to 12.

Claims (8)

1. Use of certain transition metal complexes with nitrogenous ligands as a catalyst for peroxygenated compounds, characterized in that the transition metal complexes have the formula (1) (1) M (L) n X_m meaning

M

an atom of a metal taken between the set formed by Mn, Fe, Co, Ni, Mo, W,

L

a ligand taken between the set formed by pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine or lutidine, which are unsubstituted or they can be substituted with one or two alkyl groups C_ {1} -C_ {4}.

X

chloride, bromide, nitrate, perchlorate, sulfate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of a organic acid with 1 to 22 carbon atoms,

n

means a number from 2 to 4 and m means a number from 0 to 4.

2. Use of bis (pyridine) dichloro-iron (II), bis (pyridine) dichloro-manganese (II), such as bis (morpholine) dichloro-iron (II), bis (morpholine) dichloro-manganese (II), bis (methyl imidazole) dichloro-iron  (II), bis (methyl imidazole) dichloro manganese (II), bis (ethyl-imidazole) dichloro-iron (II), bis (ethyl-imidazole) dichloro-manganese  (II), bis (pyrazole) dichloro-manganese (II), bis (pyrazole) dichloro-iron (II),  bis (pyridine) dibromo-iron (II), bis- (pyridine) -dibromo-manganese (II), bis (pyridine) diacetate-iron (II) or bis (pyridine) diacetate manganese (II) as a catalyst for peroxygenated compounds 3. Use according to claim 1, characterized in that as peroxygenated compound organic peracids, hydrogen peroxide, a perborate and a percarbonate are taken, as well as mixtures thereof. 4. Use in accordance with the claim 1 in aqueous solutions for washing materials textiles, in aqueous cleaning solutions for hard surfaces and for bleaching color spots. 5. Use according to claim 1, characterized in that simultaneously with the complex compound of formula 1 a compound that releases a peroxocarboxylic acid is used under perhydrolysis conditions. 6. Washing, bleaching and cleaning containing a transition metal complex of the Formula 1 according to claim 1. 7. Washing, bleaching and cleaning containing from 0.0025 to 1% by weight, in particular of 0.01% by weight to 0.1% by weight of a metal complex of transition of formula 1 according to claim 1. 8. Washing, bleaching and cleaning containing a transition metal complex of the formula 1 according to claim 1, as well as 1 to 10% by weight, in particular from 2% by weight to 6% by weight of a compound which releases a peroxocarboxylic acid under conditions of perhydrolysis